3-((S)-4-methyl-1-nitropentan-2-yl)pentane-2,4-dione | 1020665-85-3

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-((S)-4-methyl-1-nitropentan-2-yl)pentane-2,4-dione
• 英文别名: (S)-3-(4-methyl-1-nitropentan-2-yl)pentane-2,4-dione；3-[(2S)-4-methyl-1-nitropentan-2-yl]pentane-2,4-dione
• CAS: 1020665-85-3
• 化学式: C₁₁H₁₉NO₄
• 分子量: 229.276
• InChiKey: MFWLZGMKCOAMBH-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  16
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  80
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  4-甲基-1-硝基戊烷-2-醇 在 3-{[3,5-bis(trifluoromethyl)benzyl]amino}-4-{[(R,R)-2-( piperidine-1-yl)cyclohexyl]amino}cyclobut-3-ene-1,2-dione 、 N,N'-二环己基碳二亚胺 、 copper(l) chloride 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 124.0h， 生成 3-((S)-4-methyl-1-nitropentan-2-yl)pentane-2,4-dione
  参考文献：
  名称：

  对映选择性将1，3-二羰基化合物迈克尔加成至手性方酰胺催化的硝基烯烃上–这是普瑞巴林合成中的关键步骤†

  摘要：

  不对称的有机催化1，4-加成提供了访问大量生物学相关化合物的途径。手性方酰胺能有效地催化1,3-二羰基化合物向脂肪族硝基烯烃的对映选择性迈克尔加成反应。以高收率和高对映体纯度获得所得的γ-硝基羧酸衍生物。量子化学计算帮助我们设计了一个过渡态模型，该模型解释了所观察到的加成过程的立体化学过程。用Meldrum酸作为供体可获得最佳结果，迈克尔加合物的对映体纯度为97：3 er。采用这种方法，分三步合成了普瑞巴林，总产率为52％。

  DOI：

  10.1039/c3ob41709c

文献信息

• Doubly stereocontrolled asymmetric conjugate addition of acetylacetone to nitroolefins catalyzed by bifunctional tertiary amine–thiourea catalysts derived from both acyclic α-amino acids and carbohydrates
  作者：Xue-Wei Pu、Fang-Zhi Peng、Hong-Bin Zhang、Zhi-Hui Shao

  DOI：10.1016/j.tet.2010.03.081

  日期：2010.5

  preparative, cheap, and fine-tunable bifunctional chiral tertiary amine–thiourea organocatalysts have been developed by combining both acyclic diamines derived from acyclic α-amino acids and carbohydrates. These organocatalysts promoted the enantioselective conjugate addition of acetylacetone to various nitroolefins in good yields (up to 93%) with good enantioselectivities (up to 91% ee). The present research

  通过结合衍生自无环α-氨基酸的无环二胺和碳水化合物，开发了一种新型的易于制备，廉价且可微调的双官能手性叔胺-硫脲有机催化剂。这些有机催化剂以良好的对映选择性（高达91％ee）促进了乙酰丙酮向各种硝基烯烃的对映选择性共轭加成，收率很高（高达93％）。本研究表明将两个立体控制结构合并到一个催化剂中的优点。值得注意的是，它为手性有机分子的催化不对称合成提供了一种简单方便的双立体控制方法。
• Asymmetric Conjugate Addition of Acetylacetone to Nitroolefins with Chiral Organocatalysts Derived from Both α-Amino ­Acids and Carbohydrates
  作者：Xuewei Pu、Penghui Li、Fangzhi Peng、Xiaojiao Li、Hongbin Zhang、Zhihui Shao

  DOI：10.1002/ejoc.200900547

  日期：2009.9

  chiral tertiary amine thioureas derived from both α-amino acids and carbohydrates were developed. These organocatalysts promoted the enantioselective conjugate addition of acetylacetone to various aromatic and aliphatic nitroolefins at room temperature in good yields (up to 93 %) and with good enantioselectivity (up to 90 % ee). Furthermore, an interesting matched–mismatched effect of two different

  开发了衍生自 α-氨基酸和碳水化合物的双功能手性叔胺硫脲。这些有机催化剂在室温下以良好的产率（高达 93%）和良好的对映选择性（高达 90% ee）促进了乙酰丙酮与各种芳香族和脂肪族硝基烯烃的对映选择性共轭加成。此外，公开了手性有机催化剂中两种不同手性单元的有趣匹配-错配效应。只需将溶剂从 THF 改为甲苯，就可以使用“匹配”和“错配”手性有机催化剂以几乎相同的对映体过量获得产物的两种对映体。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Enantio- and Diastereoselective Asymmetric Addition of 1,3-Dicarbonyl Compounds to Nitroalkenes in a Doubly Stereocontrolled Manner Catalyzed by Bifunctional Rosin-Derived Amine Thiourea Catalysts
  作者：Xianxing Jiang、Yifu Zhang、Xing Liu、Gen Zhang、Luhao Lai、Lipeng Wu、Jiannan Zhang、Rui Wang

  DOI：10.1021/jo9009276

  日期：2009.8.7

  rosin-derived amine thiourea catalysts were designed and synthesized. The doubly stereocontrolled asymmetric addition of a variety of 1,3-dicarbonyl compounds to nitroalkenes was investigated. These rosin-derived chiral thioureas have been shown to serve as effective catalysts for this double-sterecontrolled organocatalytic process by the investigation of the efficacy of the thiourea catalysts in comparison with

  从可商购的天然松香衍生物开始，设计并合成了一类双官能松香衍生的胺硫脲催化剂。研究了将多种1,3-二羰基化合物双立体控制的不对称加成到硝基烯烃中。通过研究硫脲催化剂与已报道的其他硫脲催化剂的功效，已证明这些松香衍生的手性硫脲可作为该双酯控制的有机催化方法的有效催化剂。另外，这些手性硫脲配体容易获得。此外，
• Chiral amine-thioureas bearing multiple hydrogen bonding donors: highly efficient organocatalysts for asymmetric Michael addition of acetylacetone to nitroolefins
  作者：Chun-Jiang Wang、Zhi-Hai Zhang、Xiu-Qin Dong、Xiao-Jun Wu

  DOI：10.1039/b718949d

  日期：——

  New bifunctional organocatalysts amine-thioureas bearing multiple hydrogen bonding donors were synthesized and applied in catalytic asymmetric Michael addition of acetylacetone to aryl and alkyl nitroolefins. Multiple hydrogen bonding donors play a significant role in accelerating reactions, improving yields and enantioselectivities.

  合成了具有多个氢键供体的新型双功能有机催化剂胺-硫脲，并将其用于乙酰丙酮催化芳基和烷基硝基烯烃的不对称迈克尔加成反应。多个氢键供体在加速反应，提高产率和对映选择性方面起着重要作用。
• Organocatalytic Enantioselective Michael Addition of 2,4-Pentandione to Nitroalkenes Promoted by Bifunctional Thioureas with Central and Axial Chiral Elements
  作者：Fang-Zhi Peng、Zhi-Hui Shao、Bao-Min Fan、He Song、Gan-Peng Li、Hong-Bin Zhang

  DOI：10.1021/jo800774m

  日期：2008.7.1

  Two novel bifunctional amine-thiourea organocatalysts 1 and 2, which both bear central and axial chiral elements, have been developed to promote enantioselective Michael reaction between 1,3-dicarbonyl compounds and nitro olefins. The catalyst 2 afforded the desired products with good levels of enantioselectivity (up to 96% ee), showing clearly that two chiral elements of 2 are matched, and enhance the stereochemical control.